Quantum supercapacitor

ABSTRACT

A quantum supercapacitor having nanostrucutured material located between electrodes. The material includes clusters with tunnel-transparent gaps. The clusters have sizes within the range of 7.2517 nm≦r≦29.0068 nm, at which the resonant characteristics of the electron are exhibited. The size is determined by the circular radius of the electronic wave according to the formula r 0 = /(m e α 2 c)=7.2517 nm (Plank constant  , electron mass m e , fine structure constant α=1/137,036, speed of light c). The cluster size is set within the range r 0 ≦4r 0 ; the width of the tunnel-transparent gap being ≦r 0 =7.2517 nm. The energy in the supercapacitor is stored by means of controlled breakthrough of the material—a dielectric, with subsequent restoring thereof. The energy is stored uniformly along the whole volume of the material due to the resonant coupling of the electrons on the cluster. The maximum stored specific energy stored is 1.66 MJ/kg.

BACKGROUND OF THE INVENTION

1. Field of the Invention

The invention relates to the field of electronics and electrotechnologyand can be used in production of capacitors for creation of elements(cells) of memory for integrated microcircuits, in high-Q contours, indecoupling elements, and in reserve power supplies. Such memory cellscan be used as sources of current for a mobile communication facility,in energy installation of an electric vehicle, and also for bufferaccumulation of electrical energy with high specific density on theorder of 1–1.5 MJ/kg.

2. Background Art

Electrical capacitors having a large specific capacity on the base ofsolid dielectrics are known. For example the capacitor on BaTiO₃dielectrics have large permittivity ∈>1000 and specific capacity ofabout 0.3 F/cm³. However, in the majority of the power applications suchspecific capacity is not enough. To increase specific capacity differentmethods are applied. A most effective method is nanostructuring ofdielectrics such as BaTiO₃ by creation of nanosize clusters with a shell[1], or creation of thin nanosize films with metal doping [2]. With thehelp of such an approach, it is possible to increase permittivity up to∈=10⁵–10⁶ and to achieve specific capacity on the order of 100–1000F/cm³. In result, it is possible to receive specific energy reserved inthe capacitor of on the order of 2–20 MJ/kg. The specific energyreserved in such capacitors considerably exceeds one, reserved in lead(0.08 MJ/kg) and nickel (0.15 MJ/kg) electrochemical accumulators and iscommensurable with specific energy, reserved in best lithiumaccumulators (0.5MJ/kg) [3].

Obviously, the advantage of capacitors compared to electrochemicalaccumulators is rapid accumulation of energy and unlimited quantity ofthe recharging cycles. However, in capacitors made in accordance withthe foregoing patents the barium titanate with a high degree metalsdoping is used. It results in the transformation of dielectric to thesemiconductor. In result, there is large leakage current that results inrapid loss of the stored energy. Hence, the application of suchcapacitors for long-term storage of energy is not effective. Besides, asthe reserved energy increases greater than 2 MJ/kg the film BaTiO₃cracks. Thus, it is impossible to achieve a limiting value of 20 MJ/kgpractically for a while yet.

Another type of capacitors with high specific capacity is known. It isthe so-called supercapacitors which have a double electrical layerformed between liquid electrolyte and electrode. To increase thespecific capacity the electrode is made from various materials with alarge specific surface, for example [4], the patent [5]. Specificcapacity of such capacitors is on the order of 2–46 F/cm3 at the maximalspecific energy, reserved by them up to 0.045 MJ/kg. The limitingreserved energy in such capacitors is determined by potential ofelectrolyte dissociation which does not exceed 2–3 V. Such capacitorsare quickly charged and have unlimited recharging cycle. However, theelectrolyte used makes it unserviceable and also increase leakagecurrent that reduces energy storage time. Besides, the low specificreserved energy does not allow replacing by it the electrochemicalaccumulators in practically important cases.

In the listed above solid-state and liquid accumulators the mechanism ofcarry of ions is used. For example, in BaTiO₃, ions are moved togetherrelatively to a crystal lattice, and in liquid electrolyte the carry ofions is carried out due to mechanical moving of ions relative to asurface of electrodes. Such process of movement of heavy ions limits thehigh-speed characteristics. Therefore, such capacitors cannot be appliedin elements of memory of super high speed integrated circuits.

SUMMARY OF THE INVENTION

The essence of the invention is the improvement of the powercharacteristics of capacitors, their operating speed, creation of thecapacitor having small leakage current and long storage time of acharge, and also unlimited number of recharging cycles.

It is possible to solve this task by transition from a storage of acharge as ions to a storage of a charge as electrons. However, knowndielectrics, using the effect of displacement of electrons relative toions, have ∈≦100. In essence, in solid-state dielectrics theaccumulation of energy occurs due to the work of turn of a polarizationvector in a unit of dielectric volume of electronic or ionic type. Thus,maximal reserved specific energy is determined from the known equationW _(e)=½∈∈₀ E ² =U ² C/2=qU/2.  (1)

Where ∈₀—vacuum permittivity, E—electric strength in the capacitor,U—voltage in the capacitor, C—capacity of the capacitor, q—charge on thecapacitor. As it is shown by (1), it is possible to increase specificenergy by two ways: either the increase of ∈, or, more effectively, theincrease of E. However, the increase of strength of a field E results inirreversible disruption of the dielectric [6]. Disruption in soliddielectrics occurs due to electron emission in the dielectric fromcapacitor plates. The electrons, emitting in the dielectric, underaction of an accelerating electrical field, move from the cathode to theanode. On the way they have multitudinous impacts that result in theformation of an electron avalanche, i.e., disruption. As a result of theionization by collision the positive ions are created. They remain in atrace of the avalanche and form a positive charge. Besides, there is anopportunity of activization of electrons, taking place in the materialof the dielectric which also participate in avalanche disruption.Furthermore, with the increase of dielectric thickness there is aso-called bulk effect, i.e., disruptive voltage of the dielectric isreduced steeply, that results in reduction of accumulated specificenergy. The avalanche disruption results in the destruction of thematerial of the dielectric and the formation of a defective channelwhich is not restored. In result, the capacitor fails.

At present there are many theories of the mechanism of dielectricdisruption [6]. But all of them solve separate partial tasks only byapproached ways.

The essence of the invention is the creation of a new mechanism ofaccumulation of energy in all volume solid dielectrics due to themanagement of the disruption mechanism and the regeneration of workingparameters of the dielectric material.

In the disclosed invention it is proposed to use for the simultaneousincrease of ∈ and E the new mechanism of electron movement in dielectricand semiconductors in view of the spatial structure of an electron wave,published in the PCT Application [7].

In this work is shown, that the electron form—its charging wave—changesin dependence on speed of electron movement and structure of a materialin which it goes. In the simplest cases, the electron form can bepresented as charged tore, rotating about its axis. It is possible topresent an electron in a minimum of the energy as a thin uniformlycharged ring with a charge e, rotating about an axis with speed α²c,α—constant of fine structure, and c—speed of light. The electrostaticfield of such an electron is concentrated in its plane, i.e., itrepresents the transverse charged wave. In result, the cross-section ofinteraction between such electrons is minimal, and it is possible toobserve such electron state in vacuum at its movement with speedrelatively laboratory system of coordinates, less α²c or at its movementin superconductors [7]. The diameter of such electron is determined fromthe experiment of electron “tunneling” through a vacuum interval. It isexperimentally established that the tunnel effect disappears at distancebetween electrodes about 8 nm [8, chapter 9.4], [9, chapter 3]. Thisextremely important experimental fact is constantly ignored.

Consider that the radius of such a ring electron is connected withfundamental constants [7]:r ₀=

/(m _(e)α² c)=7.2517 nm.  (2)

The proposed theoretical model of a ring electron allows a new approachin describing most of time-varying and non-linear processes occurring incondensed matter with new position.

In certain materials it is possible to induce a condition of formationof a ring electron by means of an external action and/or bynanostructuring of a matter. By that, the resonance conditions foroperating of quantum supercapacitors are provided which allow itsfunctioning at normal and higher temperatures.

Due to reduction of interaction cross-section with ions of a dielectriccrystal lattice it is possible to increase working temperature of thequantum supercapacitor up to a valueT _(e) =m _(e)α³ c ²/2k=1151.86 K (878.71° C.).  (3)

The transition potential of electron through a barrier Ue=0.09928 Vcorresponds to this temperature. At coupling of electrons with theunidirectional spins, its energy grows twice.

If electrons with oppositely directed spins couple, the coupling energy,due to the spin turning in space on π, decreases up to valueT _(Π) =T _(e)/π=366.65 K (93.5° C.).  (4)

Temperatures T_(e) and T_(Π)are critical working temperatures dependingon the given mode of operations of quantum supercapacitors.

The frequency of rotation of an electronic ring will determine thelimiting working frequency of the quantum supercapacitorsf _(e)=α² c/2πr ₀ =m _(e)(α² c)² /h=3.5037*10¹¹ Hz.  (5)

Extreme achievable density of a current in the quantum supercapacitor isj _(e) =ef _(e) /πr ₀ ²=4πem _(e) ³α⁸ c ⁴ /h ³=3.4*10⁴ A/cm².  (6)

Maximum allowed field strength at which disruption occurs in the quantumsupercapacitor isE _(e) =U _(e) /r ₀ =m _(e) ²α⁵ c ³/2e

=1.37*10⁵ V/cm  (7)

The resistance of a material determines the leakage current of thecapacitor, i.e., the storage time of energy. The resistance can becalculated per one cluster as followsR _(e) =h/2e ²α=1.768*10⁶ Ω  (8)

At series connection of such clusters, the resistance grows directlyproportionally and in essence does not affect on the leakage currents ofthe capacitor if the intensity of a field is less than E_(e) and theworking temperature is less than T_(e).

To calculate power parameters of the capacitor cluster will beconsidered to be centrally symmetrical and have together with tunnelingtransparent shells the diameter of 2.175*10⁻⁶ cm. As such, 2.1*10¹¹ suchclusters are present on 1 cm² of material. The steadiest state ofcluster will be in the case when there are two electrons in it. Then 1cm3 of a material can store the charge of 2.42*10⁻² C. If a workingvoltage on capacitor plates is 1.37*10⁵ V, in compliance with theformula (1) the specific reserved energy in the capacitor isW_(e)=1.66*10³ J/cm³ If a hollow sphere is used, the specific density ofa material at any shell will not exceed 1 g/cm³. Hence, the specificenergy reserved in 1 kg of a material will be not less than 1.66 MJ/kg.This value corresponds to ∈=2*10⁶.

On the base of this model it is possible to develop the absolutely newprinciple of work and ways of functioning of capacitors with soliddielectric according to the given below formula and description of theinvention. In principle, it is possible to create any defect in a solidmaterial which will be a certain resonator for a ring wave withradius-r_(o) and effective capacitor Q−1/α. The high capacitor Q of theresonator determines the high working temperature of the capacitor.

The essence of the invention is as follows.

In accordance with one embodiment of the invention the quantumsupercapacitor contains at least two electrodes, the interval betweenwhich is filled by nanostructured materials, consisting of, at least,one cluster and a tunnel-transparent layer. It is characterised by thatthe cluster has at least one distinctive cross size, determined withinan interval7.2517 m≦r≦29.0068 nm.

The thickness of the tunnel-transparent gap is not more than 7.2517 nm,and the spacing between the electrodes is more than 7.2517 nm.

In the invention limit values are determined from the formular=a*r ₀,where r ₀ is determined as the ring radius of an electron wave accordingto the formular ₀=

/(m _(e)α² c)=7.2517 nm,where

—Plank contstant, m_(e)—electron mass, α=1/137,036—constant of finestructure, c—speed of light, and a—factor determined within the range1≦a≦4.

In the invention, the clusters could be made from material selected fromthe group consisting of the substances—semiconductor, conductor,superconductor, high molecular organic substance or their combination.

Also the clusters could be made in the form of a cavity having a shellfrom a tunnel-transparent layer consisting of the semiconductor ordielectric.

In one variant, the clusters have centrally symmetric form. In anothervariant, the clusters are extended and have a distinguishedcross-sectional size determined within the interval14.5034 nm≦r≦29.0068 nm.

Extending clusters can be placed along an axis and have a regularstructure with the period determined in intervals7.2517 nm≦r≦29.0068 nm.

According to another embodiment of the invention, a set of clusters canbe regularly located at least in one layer, and the intervals betweenclusters is tunnel-transparent and do not exceed 7.2517 nm (r₀).

Besides a set of clusters with tunnel-transparent gaps can be regularlylocated as layers, at least, in one of layers the parameters of theclusters can differ from the parameters of the clusters in the nextlayers. The intervals between the clusters are tunnel-transparent and donot exceed 7.2517 nm (r₀).

Also a set of clusters made in the form of a cavity having a shell madefrom a tunnel-transparent layer can contact at least in two points of acavity with the next clusters. Then they form the material similar tofoam with open pores. The shell is made from either semiconductor,dielectric, or high molecular organic substance, and the pores can befilled with either gas, semiconductor, or dielectric, with theproperties differing from the properties of the material of the shell.

The mode operation of the quantum supercapacitor is characterized bythat the enclosed electrical field in a working range of strength forwork of the capacitor in a storage mode should not exceed 1.37*10⁵ V/cm.It is determined from the condition E≦3E_(max), whereE _(max) =m _(e) ²α⁵ c ³/2e

=1.37*10⁵ V/cm,and the intensity of a field in a charge mode should not exceed 4.11*10⁵V/cm, accordingly from the condition E≦3E_(max).

Besides for reliable work of the quantum supercapacitor the limitingdensity of a current in it should be limited by the value 1.02*10⁵A/cm², determined from the formulaj _(e)=12πem _(e) ³α⁸ c ⁴ /h ³=1.02*10⁵ A/cm².

The way of work of the capacitor in a discharge mode is characterizedalso by that the source of a current with sign, which is opposite tosign of a field of the capacitor in a charge mode, is connected to thecapacitor through loading. It is necessary for completely taking offcharges on all depth of the capacitor. Otherwise, the capacitor isunloaded partially.

In the capacitors the limiting working frequency of management of thequantum supercapacitor achieves the valuef _(e) ⁰ =f _(e)/2=m _(e)(α² c)²/2h=1.752*10¹¹ Hz.

That is especially important to increase the capacitor processing speedused in memory. The examples of realization of these devices are givenbelow and are represented on the drawings.

BRIEF DESCRIPTION OF THE DRAWINGS

The list of figures specified on the drawings

FIG. 1. Nanoelement of quantum supercapacitors.

FIG. 2. Quantum supercapacitor with dielectric comprisingcentral-symmetric clusters.

FIG. 3 Quantum supercapacitor with dielectric comprising axis-symmetricclusters.

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

On FIG. 1 the typical nanoelement of the quantum supercapacitors isrepresented with a central-symmetric cluster 1 and a tunnel-transparentshell 2. Clusters can be axis-symmetric. It is important, that theresonant conditions of formation in them of a ring wave of electron arecarried out.

On FIG. 2 one of the variants of the quantum superccapacitors isrepresented agrees to the present invention with conducting electrodes3, 4; tunnel-transparent shell of cluster 5; and central-symmetriccavity in cluster 6. Cluster cavity 6 can be filled with an appropriatematerial or gas for creation of the formation conditions of the ringresonant electron. Tunnel-transparent shell 5 divides clusters amongthemselves and creates conditions of motion of electrons as ahomogeneous wave from the cathode to the anode. The anode and cathodeposition can be interchanged, i.e., the capacitor is not polar.

On FIG. 3 another variant of the quantum superccapacitor is representedwith conducting electrodes 7, 8; tunnel-transparent shell of cluster 9;and axis symmetric cavity in cluster 10. Cluster cavity 10 can be filledwith the appropriate material or gas for creation of conditions of ringresonant electron formation. Tunnel-transparent shell 9 divides clusteramong themselves and creates conditions of motion of electrons as ahomogeneous wave from the cathode to the anode. The anode and cathodeposition can be interchanged, i.e., the capacitor is not polar.

Each layer the capacitor shown in FIGS. 2 and 3 should be homogeneous.At the same time, the layers can differ from each other by the clustersizes or material.

According to the further improvement, the capacitor is characterizedalso by that the capacitor electrodes are made from conducting materialswith various electrical properties. In such case, the various works ofan electron output from the electrodes allow to change conditions of acharge and discharge of the capacitor. In this case discharge conditionscan be bipolar as unipolar.

EMBODIMENT OF THE INVENTION

The disclosed invention provides an opportunity of increasing specificdensity of energy content at simultaneous increase of workingtemperatures of capacitors and reduction of leakage currents, thatincreases a storage time of energy in the capacitor. These parametersdetermine a commercial realizability of capacitors. However, the problemis, whether it is possible to use modern techniques for producing theproposed capacitors and whether the mass-produced devices areeconomical.

Consider opportunities of technical realization. The creation of thedisclosed nanostructured materials for capacitors as clusters, dividedtunnel-transparent intervals is quite feasible on modern technologicalbase.

Now in the electrotechnical industry the dielectrics with the nonlinearcharacteristic are widely used, on the base of which the limiters ofinput voltage-varistors are created. In these elements have place thedischarge proceeds without any destruction of a material, for example inwide-gap semiconductors, designed in the form of ZnO multilayerpolycrystalline films. The size of crystallites-clusters in these filmsis 0.2–15.0 μm. They are divided by Bi₂O₃ tunnel-transparent gaps of thethickness 2.0–10.0 nm [10]. Manufacture of varistors is well organized.Based on the manufacture it is possible simply enough to make clustersby the size less than 200 nm, having finished them up to thecharacteristic size 14.5 nm.

In this case resonant properties of electrons will be shown and theelement will get new properties for storing energy.

There are two methods of forming spherical and sphere-like particles[11]. The first method—metal or semiconductor clusters of a diameter upto 37 nm are formed from a gas phase with their further oxidation in theoxygen flow or similar chemicals. Formation of such particles is similarto formation of hail in the Earth atmosphere. The second method is thecolloidal method. It is based on cluster precipitation from metal saltsolutions followed by chemical coating with corresponding enclosures.

Nanosized hollow spheres of zirconium dioxide are automatically obtainedduring the process of high-frequency plasma-chemical denitrification;therefore they may be applied to the substrate directly from plasma[12]. Or, for example, 4—15 nm particles result automatically inmaterial Mo₂N [13].

Designing planar vertical nanochannels is based on collective formationmethods, e.g. according to electrochemical oxidation Al, Ta, Nb, Hf,etc. The formed channel may be filled with metal or semiconductor by thegalvanic technique [14].

The aforementioned examples show that the modern techniques allowproduction of nanostructured materials for the quantum supercapacitor onthe basis of existing technologies.

Besides in microelectronics there are fulfilled ways of creation onsilicon gigabite memory. It is possible to apply nanostructured materialto increase storage time and reduce the sizes of cells of such memory.It can directly be plated on cells of memory from a gas phase throughopen windows of a mask. In this case it is possible on the same surfaceof silicon to receive greater volume of memory or its smaller powerconsumption.

It is especially important, that it is possible to receive non-volatilememory. Thus the minimally possible cells of memory for the perspectiveintegrated circuits will not exceed the size one cluster with a shell,i.e., about 30 nm.

It is important, that this size is a fundamental limit for theelectronic circuits using electrons as carriers. Below than this size itis impossible to create elements of the integrated circuits due totunnel effects appearing between control lines.

As applied to power engineering for buffer accumulation of a volumeenergy it is possible to use for creating quantum supercapacitors moresimple technology of making of nanostructured material, for example, onthe base of creation nanoporous foam. For this purpose, it is possibleto finish technology of creation of carbon foam or technology ofsynthesis of nanoporous silicate glasses [15]. Besides the low-coastmethod of synthesis of spherical porous particles on sol-gel method willallow also to generate nanostructured material for the capacitor [16].

INFORMATION SOURCES

-   1. U.S. Pat. No. 5,856,907-   2. U.S. Pat. No. 6,180,252-   3. Electrochemistry. Past thirty and next thirty years. G. Bluma.    M., World, 1982 (In Russian).-   4. U.S. Pat. Nos. 4,697,224; 5,557,497-   5. Russian Patent 2160940-   6. PCT/BY99/00012 “Quantum-Size Electronic Devices and Operating    Conditions Thereof” (International Publication Number: WO 00/41247,    13.07.2000)-   7. M. Beyer, W. Boeck, K. Moller, W. Zaengl. Hochspannungstechnic.    Theoretische und Praktische Grundlagen. Springer-Verlag, 1986.-   8. S. M. Sze. Physics of Semiconductor Devices. A Wiley-Interscience    Publication John Wiley&Sons. New York. 1981-   9. Buzaneva E. V. Microstructures of integral electronics. M. Radio.    1990.-   10. Application PCT WO 98/21754, 22.05.1998.-   11. Petrov U. I. Cluster and minor particles. M. Nauka. 1986, 368    pp. Dedov N. V. et al., Structural studies of powders on basis of    zirconium dioxide produced by HF-plasmachemical denitration method.    Glass and Ceramics. 1991. No. 10, p. 17–19. J. Phys. Chem. 18.    No. 15. 1994. P. 4083.-   12. Averianov E. E. Anodization manual, M., Mashinostroenie, 1988    U.S. Pat. No. 5,300,272-   13. Anal. Sci. 10. No. 5. 1994. P. 737.

1. A quantum supercapacitor comprising at least two electrodes, theinterval between which is filled by nanostructured materials, includingat least one cluster with a tunnel-transparent gap, wherein each clusterhas a characteristic size determined in the range 7.2517 nm ≦r ≦29.0068nm, the thickness of each tunnel-transparent gap being less than orequal to 7.2517 nm, the spacing between the electrodes being more than7.2517 nm.
 2. The quantum supercapacitor according to claim 1, whereinthe clusters are made of material having a substance selected from thegroup of semiconductor, conductor, superconductor, high molecularorganic substance or their combination.
 3. The quantum supercapacitoraccording to claim 1, wherein the clusters are made in the form of acavity having a shell made of a tunnel-transparent layer, the shellbeing either a semiconductor or a dielectric.
 4. The quantumsupercapacitor according to claim 1, wherein each cluster has acentrally symmetric form.
 5. The quantum supercapacitor according toclaim 1, wherein each cluster is extended and has a characteristic sizedetermined within the range
 14. 5034 nm ≦r ≦29.0068 nm.
 6. The quantumsupercapacitor according to claim 4, wherein each cluster is extendedalong an axis and has a regular structure with a period determinedwithin the range 7.2517 nm ≦r ≦29.0068 nm.
 7. The quantum supercapacitoraccording to claim 1, wherein a set of the clusters are located at leastin one layer, and the spacings between adjacent clusters aretunnel-transparent less than or equal to
 7. 2517 nm.
 8. The quantumsupercapacitor according to claim 1, wherein a set of the clusters withtunnel-transparent gaps are located as layers, at least in one of thelayers the parameters of the clusters differ from the parameters of theclusters in other layers, the spacings between the adjacent clusters aretunnel-transparent less than or equal to 7.2517 nm.
 9. The quantumsupercapacitor according to claim 1, wherein a set of the clusters aremade in the form of a cavity having a shell made of a tunnel-transparentlayer, contact at least in two points of a cavity with the adjacentclusters, forming the material similar to foam with open pores, eachshell is made from either semiconductor, dielectric, or high molecularorganic substance, and pores of which can be filled either with gas,semiconductor, or dielectric, with properties differing from propertiesof material of the shell.
 10. The quantum supercapacitor according toclaim 1 wherein the electrodes are made from conducting materials withvarious electrical properties.
 11. The quantum supercapacitor accordingto claim 1, wherein each cluster has an axis symmetric form.
 12. Thequantum supercapacitor according to claim 2 wherein the electrodes aremade from conducting materials with various electrical properties. 13.The quantum supercapacitor according to claim 3 wherein the electrodesare made from conducting materials with various electrical properties.14. The quantum supercapacitor according to claim 4 wherein theelectrodes are made from conducting materials with various electricalproperties.
 15. The quantum supercapacitor according to claim 5 whereinthe electrodes are made from conducting materials with variouselectrical properties.
 16. The quantum supercapacitor according to claim6 wherein the electrodes are made from conducting materials with variouselectrical properties.
 17. The quantum supercapacitor according to claim7 wherein the electrodes are made from conducting materials with variouselectrical properties.
 18. The quantum supercapacitor according to claim8 wherein the electrodes are made from conducting materials with variouselectrical properties.
 19. The quantum supercapacitor according to claim9 wherein the electrodes are made from conducting materials with variouselectrical properties.